Polyamido bis-n-alkyl piperazines



United States Patent Olfice 3,505,335 POLYAMIDO BIS-N-ALKYL PIPERAZINES Dwight E. Peerman, Minneapolis, Minn., assignor to General Mills, Inc., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 460,460, June 1, 1965. This application Jan. 21, 1969, Ser. No. 792,808

Int. Cl. C07d 51/70 US. Cl. 260-268 6 Claims ABSTRACT OF THE DISCLOSURE New compounds having the formula:

GHQ-CH2 N-Z GHQ-Q.

ll H N--COH CHq-N where Z is This application is a continuation-in-part of my earlier application Ser. No. 460,460, filed June 1, 1965, and now abandoned.

The present invention relates to new diadducts of acrylamide and certain heterocyclic compounds. These new compounds are excellent curing agents for epoxy resins. The rate of reaction with epoxy resins is such that it is possible to combine the diadducts of the present invention with epoxy resins, obtain a homogeneous melt, and quench the mixture immediately or after such degree of partial reaction as is desired is accomplished. The resulting quenched mixture or partially reacted combination will then cure to completion rapidly when the temperature is again elevated.

By B-stage is meant a partially cured intermediate stage in which the two reactants (i.e. the curing agent and epoxy resin) are homogeneously compatible in a stable single phase ready for final cruing at elevated temperatures. The curing of the epoxy resin may be considered as proceeding through three stagesA, B and C. The A- stage is a simple blend or mixture of the epoxy resin and the curing agent in which essentially no reaction has taken place. With the compounds of the present invention as the curing agents, such simple blends or mixtures will be stable for extended periods of time.

The B-stage is the same mixture which has been partially reacted or cured and is stable for extended periods of time. The B-stage resin can be cured at elevated temperatures to yield the finally cured stage, the C-staged, which is an insoluble and infusible polymer. The partial curing can be effected at various temperatures. At higher temperatures the time of heating becomes short, while at lower temperatures the heating period is slightly longer and controll is easier. In general, it is preferred to B- stage resins with the compounds of the present invention at temperatures of 100 to 150 C. which usually requires a time period of minutes to 30 seconds.

3,505,335 Patented Apr. 7, 1970 In addition to the ability to control the pot life of these compositions and to produce B-stage resins, the present invention provides new compounds which cure epoxy resins without the liberation of volatile by-products which tend to produce gas bubbles in the curing resin system.

It is, therefore, an object of the present invention to provide novel acrylamide adducts of certain heterocyclic compounds. This and other objects will become apparent from the following detailed description.

The new compounds of the present invention are produced by reacting acrylamide with piperazine or a derivative thereof in a molar ratio of approximately 2:1. The useful heterocyclic compounds have the formula:

where X is H or (CH n is 1, 2 or 3 and R is NH or Representative of such heterocyclic compounds are piperazine, aminoethyl piperazine, aminopropyl piperazine, 4-di(bispiperidyl) propane, 4-di(bispiperidyl) methane and the like.

Reaction may be carried out in any of a variety of ways, but preferably the acrylamide is dissolved in a solvent such as methanol and the reaction mixture then heated to reflux temperature. The heterocyclic compound is then added slowly and the reaction mixture maintained at reflux temperature until the reaction is complete. Thereafter the solvent is removed by distillation to yield the final product which, in most instances, is either solid or semi-solid. The acrylamide adds to the secondary amine nitrogens of piperazine and compounds such as 4-di(bispiperidyl) propane. In the case of compounds such as aminoethyl piperazine, the acrylamide adds one mole to the primary amine nitrogen and one mole to the secondary amine nitrogen in the ring. The compounds of the invention have the theoretical, idealized structural formula:

II where Z is CH CH -C-NH; or (C 2)n R, n is 1, 2 or 3 and As indicated above, my new compounds are useful for curing epoxy resins in general. The epoxy resins comprise those materials possessing more than one vicinal epoxy group, i.e., more than one group. These compounds may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and may be substituted, if desired, with non-interfering substituents such as chlorine, hydroxyl groups, ether radicals and the like. The polyepoxides may be monomeric or polymeric. The epoxy group may be terminal or non-terminal For clarity, many of the polyepoxides will be referred to hereinafter in terms of their epoxy equivalency. The term epoxy equivalency refers to the number of epoxy groups contained in the average molecule of the desired material. The epoxy equivalency is obtained by dividing the average molecular weight of the polyepoxide by the epoxide equivalent weight. The epoxide equivalent weight is determined by heating one gram sample of the polyepoxide with an excess of pyridinium chloride dissolved in pyridine at the boiling point for 20 minutes. The excess pyridinium chloride is then back-titrated with 0.1 N sodium hydroxide to the phenolphthalein end point. The epoxide value is calculated by considering one HCl as an equivalent of one epoxide. This method is used to obtain all epoxide values reported herein, unless otherwise stated.

If the polyepoxides are single monomeric compounds having all of their epoxide groups intact, their epoxy equivalency will be whole integers, such as 2, 3, 4 and 5. However, in the case of the polymeric-type polyepoxides, many of the materials may contain some of the monomeric monoepoxides or have some of their epoxy groups hydrated or otherwise reacted and/or contain macromolecules of somewhat diflFerent molecular weight so the epoxy equivalent values may be quite low and contain fractional values. The polymeric material may, for example, have epoxy equivalent values, such as 1.5, 1.8, 2.5 and the like.

The monomeric-type polyepoxide compounds may be exemplified by the following: vinylcyclohexene dioxide, epoxidized soybean oil, butadiene dioxide, 1,4-bis(2,3- epoxypropoxy) benzene, 1,3-bis,2,3-epoxypropoxy) benzene, 4,4'-bis(2,3-epoxypropoxy) diphenyl ether, 1,8-bis- (2,3-epoxypropoxy) octane, 1,'4-bis(2,3-epoxypropoxy)cyclohexane, 4,4-bis (2-hydroxy-3,4-epoxybutoxy) diphenyldimethylmethane, 1,3-bis(4,5-epoxypentoxy)-5-chlorobenzene, 1,4-bis(3,4-epoxybutoxy)-2-chlorocyclohexane, diglycidyl ether, 1,3-bis(2-hydroxy-3,4-ep0xybutoxy) benzene, 1,4-bis(2-hydroxy-4,5-epoxypentoxy) benzene, 1,2, 5,6-di-epoxy-3-hexyne, l,2,5,6-di-epoxyhexane, and 1,2,3, 4-tetra(2-hydroxy-3,4-epoxybutoxy) butane.

Other examples of this type include the glycidyl polyethers of the polyhydric phenols obtained by reacting a polyhydric phenol with a great excess, e.g., 4 to 8 mol excess, of a halogen-containing epoxide in an alkaline medium. Polyhydric phenols that can be used for this purpose include bis-phenol, resorcinol, catechol, hydroquinone, methyl resorcinol, or polynuclear phenols, such as 2,2-bis(4-hydroxyphenyl) butane, 4,4'-dihydroxybenzophenone, bis(4-hydroxyphenyl) ethane, and 1,5-di-hydroxynaphthalene. The halogen-containing epoxides may be further exemplified by 3chloro-1,2-epoxybutane, 3- bromo-1,3-epoxyhexane, 3-chloro-1,2-epoxyoctane and the like.

Examples of the polymeric-type polyepoxides include the polyepoxypolyhydroxy polyethers obtained by reacting, preferably in an alkaline or an acid medium, a polyhydric alcohol or polyhydric phenol with a polyepoxide, such as the reaction product of glycerol and bis(2,3-epoxypropyl) ether, the reaction product of sorbitol and bis(2,3-epoxy- Z-methylpropyl) ether, the reaction product of pentaerythritol and 1,2-epoxy 4,5-epoxypentane, the reaction product of bis-phenol and bis(2,3-epoxy-2-methylpropyl) ether, the reaction product of resorcinol and bis(2,3-epoxypropyl) ether, and the reaction product of catechol and bis- (2,3-epoxypropyl) ether.

A further group of the polymeric polyepoxides comprises the hydroxy-substituted polyepoxides polyethers obtained by reacting, preferably in an alkaline medium, a slight excess, e.g., 0.5 to 3 mol excess, of a halogencontaining epoxide as described above, with any of the aforedescribed polyhydric phenols, such as resorcinol, catechol, bis-phenol, bis(2,2'-dihydroXy-dinapthyl) methane and the like.

Also included within this group are the polyepoxy polyethers obtained by reacting, preferably in the presence of an acid-acting compound, such as hydrofluoric acid, one of the aforedescribed halogen-containing epoxides with a polyhydric alcohol, such as glycerol, propylene glycol, ethylene glycol, trimethyleneglycol, butylene glycol and the like, and subsequently treating the resulting product with an alkaline component.

Other polymeric polyepoxide compounds include the polymers and copolymers of the epoxy-containing monomers possessing at least one polymerizable ethylenic linkage. When this type of monomer is polymerized in the substantial absence of alkaline or acidic catalysts, such as in the presence of heat, oxygen, peroxy compound, actinic light and the like, they undergo addition polymerization at the multiple bond leaving the epoxy group unaffected. These monomers may be polymerized with themselves or with other ethylenically unsaturated monomers, such as styrene, vinyl acetate, methacrylonitrile, acrylonitrile, vinyl chloride, vinylidene chloride, methyl acrylate, methyl methacrylate, diallyl phthalate, vinyl allyl phthalate, divinyl adipate, chloroallyl acetate, and vinyl methally pimeate. Illustrative examples of these polymers include poly- (allyl-2,3-epoxypropyl ether), poly(2,3-epoxypropyl crotonate), allyl-2,3-epoxypropyl etherstyrene copolymer, methallyl-3,4-epoxybutyl ether-allyl benzoate copolymer, poly- (vinyl-2,3-epoxypropyl ether), allyl glycidyl ether-vinyl acetate copolymer and poly(4-glycidyloxystyrene).

Examples of non-terminal polyepoxides include epoxidized esters of polyethylenically unsaturated monocarboxylic acids, such as epoxidized lineseed, soybean, perilla, oiticia, tung, walnut and dehydrated castor oil, methyl linoleate, butyl linOleate, ethyl 9,12-octadecadienoate, butyl 9,12,15-octadecatrienoiate, butyl elesostearate, monoglycerides of tung oil fatty acids, monoglycerides of soybean oil, sunflower, rapeseed, hempseed, sardine, cottonseed and the like.

Another group of non-terminal polyepoxides includes the epoxidized esters of unsaturated monohydric alcohols and polycarboxylic acids, such as, for example, di(2,3- epoxybutyl) adipate, di(2,3-epoxybutyl) oxalate, di(2,3- epoxyheptyl) succinate, di(2,3-epoxybutyl) maleate, di (2,3-epoxyoctyl) pimelate, di(2,3-epoxypropyl) phthalate, di(2,3-epoxycyclohexyl) adipate, di(2,3-epoxypentyl) thiodipropionate, di(5,-6-epoxytetradecyl) diphenyldicarboxylate, di(3,4-epoxyhepty1) sulfonyldibutyrate, tri(2,3- epoxypropyl)1,2,4-butanetricarboxylate, di(5,6-epoxypentadecyl) tartarate, di(4,5-epoxytetradecyl) maleate, di- (3,4-epoxybutyl) citrate, and di(4,5-epoxyoctadecyl) malonate. Preferred members of this group comprise the glycidyl esters, such as the glycidyl esters of the dicarboxylic acids preferably containing from 2 to 18 carbon atoms, such as diglycidyl phthalate, diglycidyl maleate, diglycidyl adipate, diglycidyl sebacate, diglycidyl cyclohexanededicarboxylate and the like.

Another group of the polyepoxides includes the epoxidized esters of unsaturated alcohols and unsaturated carboxylic acids, such as 2,3-epoxy-butyl 3,4-epoxypentanoate, 3,4-epoxyhexyl 3,4-epoxypentanoate, 3,4-epoxycyclohexyl 3,4-epoxycyclohexanoate, 3,4-epoxycyclohexyl 4,5-epoxyoctanoate, 2,3-epoxycyclohexylmethyl epoxycyclohexane carboxylate.

Still another group of the epoxy-containing materials includes epoxidized derivatives of polyethylenically unsaturated polycarboxylic acids such as, for example:

dimethyl 8,9,12,13-diepoxyeiconsanedioate,

dibutyl 7,8,1 1,12-diepoxyoctadecanedioate,

dioctyl 10,1 1-diethyl-8,9,12,13-diepoxyeiconsanedioate,

dihexyl 6,7,10, 1 1-diepoxyhexadecanedioate,

didecyl '9-epoxy-ethyl-10,1l-epoxyoctadecanedioate,

dibutyl 3-butyl-3,4,5,6-diepoxycyclohexane-1,2-

dicarboxylate,

dicyclohexyl 3,4,5,6-diepoxycyclohexane-1,2-dicarboxylate,

dibenzyl 1,2,4,S-diepoxycyclohexane-1,2-dicarboxylate and diethyl 5,6,10,1l-diepoxyoctadecyl succinate.

Still another group comprises the epoxidized polyesters obtained by reacting an unsaturated polyhydric alcohol and/or unsaturated polycarboxylic acid or anhydride groups, such as, for example, the polyester obtained by reacting 8,9,12,13-eicosadienedioic acid with ethylene glycol, the polyester obtained by reacting diethylene glycol with Z-cyclohexene-1,4-dicarboxylic acid and the like, and mixtures thereof.

Still another group comprises the epoxidized polyethylenically unsaturated hydrocarbons, such as epoxidized 2,2- bis(2-cyclohexenyl) propane, epoxidized vinyl cyclohexane and epoxidized dimer of cyclopentadiene.

Another group comprises the epoxidized polymers and copolymers of diolefins, such as butadiene. Examples of this include, among others, butadiene-acrylonitrile copolymers (Hycar rubbers), butadiene-styrene copolymers and the like.

Particularly preferred epoxy-containing organic materials to be cured with the compounds of the present invention are the members of the group consisting of the organic compounds possessing a plurality of epoxyalkoxy radicals, e.g., two to four, joined to an organic radical which contains from one to two aromatic rings, organic compounds possessing a plurality of epoxyhydroxyalkoxy radicals, e.g., two to four, joined to an organic radical containing from one to two aromatic rings, the polyepoxy-containing polymeric reaction product of an aromatic polyhydric phenol and epihalohydrin, the polyepoxy-containing polymeric reaction product of an aliphatic polyhydric alcohol and epichlorohydrin, the polyepoxy-containing polymeric reaction product of a polyhydric phenol and a polyepoxide compound, the polyepoxy-containing polymeric reaction product of an aliphatic polyhydric alcohol and a polyepoxide compound, the polymers of the epoxy-containing monomers possessing at least one polymerizable ethylenic linkage prepared in the absence of alkaline or acidic catalysts, and copolymers of the foregoing epoxy-containing monomers and a monomer containing at least one CH =C= group prepared in the absence of alkaline or acidic catalysts. The expression epoxyalkoxy radical refers to an alkoxy radical substituted with an epoxy group. The expression epoxyhydroxyalkoxy radica refers to an alkoxy radical substituted with a hydroxyl and epoxy group.

Coming under special consideration, particularly because of the fine quality of coatings prepared from their resinous products are the monomeric and polymeric-type glycidyl polyethers of dihydric phenols obtained by reacting epichlorohydrin with a dihydric phenol in an alkaline medium. The monomeric products of this type may be represented by the general formula:

wherein R represents a divalent hydrocarbon radical of the dihydric phenol. The polymeric products will generally not be a single simple molecule but will be a complex mixture of glycidyl polyethers of the general formula:

wherein R is a divalent hydrocarbon radical of the dihydric phenol and n is an integer of the series 0, l, 2, 3, etc. While for any single molecule of the polyether rr is an integer, the fact that the obtained polyether is a mixture of compounds causes the determined value for n to be an average which is not necessarily zero or a whole number. The polyethers may in some cases contain a very small amount of material with one or both of the terminal glycidyl radicals in hydrated form.

The aforedescribed preferred glycidyl polyethers of the dihydric phenols may be prepared by reacting the required proportions of the dihydric phenol and the epichlorohydrin in an alkaline medium. The desired alkalinity is obtained by adding basic substances, such as sodium or potassium hydroxide, preferably in stoichiometric excess, to the epichlorohydrin. The reaction is preferably accomplished at temperatures within the range of from 50 to 150 C. The heating is continued for several hours to effect the reaction and the product is then washed free of salt and base.

Preferred members of the above-described group of polyepoxides are the glycidyl polyethers of the dihydric phenols, and especially 2,2-bis(4-hydroxyphenol) propane (i.e. Bisphenol A), having an epoxy equivalency between 1.0 and 2.0 and a molecular Weight between 900 and 2900. Particularly preferred are those having a Durrans mercury method softening point of at least about 100 C.

Another suitable group of polyglycidyl ethers are the polyglycidyl ethers of alpha,alpha-omega,omega-tetrakis (hydroxyaryl) alkanes. This group of compounds is described and illustrated in US. 2,806,016 to Schwarzer. The polyglycidyl ether prepared as in Example I of said patent has a melting point of about C. and contains 0.452 epoxy equivalent per grams.

The following examples will serve to illustrate the invention:

EXAMPLE I Acrylamide (2 mols), 142 grams, was dissolved in methanol and brought to the reflux temperature. To this was added slowly aminoethyl piperazine (1 mol), 129 grams, also dissolved in methanol. After it was complete the reactants were agitated and refluxed for an additional 60 minutes. The methanol was then stripped ofl under vacuum and the product collected. It was a white solid having the following analysis: Amino No. 609 (theor. Amine No. 621), percent N 24.5 (theor. percent N 25.8). It had the formula:

(I) G H:- C Hz /H HzN(i-CH2CHz-N N-CHZOHl-N CHz-CH: CHzCHrC-NH:

EXAMPLE II The diacrylamide adduct of piperazine was prepared by refluxing in methanol 2 mols (142 g.) of acrylamide with 1 mol (86 g.) of piperazine for one hour. After vacuum stripping, the white solid analyzed as follows: Amine No. =486 (Theor.=475); percent N=24.5 (Theor.=27.1); and M.P.=230 C. It had the formula:

3 C 112- 0 H2 HzN-C-CH CHz-N N-OHzCHz-O-NH:

CHzCHz The following examples illustrate the use of the compounds of the present invention as curing agents for epoxy resins.

EXAMPLE A The curing agent of Example I was blended with an epoxy resin derived from Bisphenol A and epichlorohydrin having an epoxy equivalent weight of 925, in three diiferent ratios, namely, 32.3 grams of curing agent to 267.7 grams of epoxy resin, 38.3 grams of curing agent to 261.7 of epoxy resin and 44.3 grams of curing agent to 255.7 grams of epoxy resin. These blends were designated Nos. 1, 2 and 3 respectively. No. 1 gelled in 60 seconds at C. and 30 seconds at 205 C. No. 2 gelled in 75 seconds at 150 C. and 35 seconds at 205 C. No. 3 gelled at 45 seconds at 150 C. and 25 seconds at 205 C. There was no bubbling in the film as might be caused by reversal of the reaction and the liberation of volatile by-product. The cure time of this material was found to be 3 minutes at 232 C., at the end of which time it passed the extensibility test.

7 EXAMPLE B of 525) 4460 N,N'-bis(3-propioam'ide) aminoethylpiperazine (of Example I) 790 Powdered mica 1580 Amorphous silica 211 The powdered mica is intended for thermal resistance and the amorphous silica is intended as a flow control agent. The epoxy resin was melted in a Baker-Perkins dispersion blade blender and maintained at 120 C. The curing agent was added and blended for 1 /2 minutes. The entire mass was poured over Dry Ice to cool quickly. This material was then pulverized to produce a solid powdered coating suitable for fluid bed application and for other methods of application. A square probe measuring A inch by "7 inch by 4 inches was coated with this composition and the composition cured in 2 to 3 minutes at 232 C. The percentage of coating on the edge as compared to that on the flat was 68%. The coated probe had a cut through temperature on the edge of more than 238 C.

EXAMPLE C The coating powder formulated in Example B Was used to coat -inch electric motor stators in a commercial spray coating machine. This machine put on the stator a fused film thickness of 11-16 mils of coating composition. On the corners, the coating was from 4-7 mils thick. The average edge coverage on the stators with this powder was near 45%. The best edge coverage achieved on a single stator was 60%.

A variability study on the coating thickness on stators was conducted with these machine-coated stators. Measuring pieces cut from 5 stators the variance of the coating thickness on the flats was about 3, the variance of the coating thickness on the corners was less than 1, and the variance in percentage edge coverage was approximately 50. This variance compares very favorably with the variance in percent edge cover achieved by two commercial coating powders applied on this same coating machine. In each case, the variance in percent edge cover was over 100 with these commercial products.

EXAMPLE D A stator coating powder was formulated using the following amounts of the following ingredients:

The silicone resin is intended as an anti-cratering agent. The procedure used in formulating this stator coating powder was similar to that used in Example C. This powder gelled at 150 C. in 3 minutes and at 205 C. in 1 minute. When coated by the fluidized bed process on a steel probe, the coating was smooth and glossy with only a slight waviness on its surface. It had 62% edge coverage on a square probe and had a cut through temperature greater than 238 C. The cure time at 232 C. was 3-4 minutes. Several steel probes were coated with this powder and cured for 10 min. at 232 C. The probes were then immersed in the following solvents and chemicals:

Water 10% critric acid Aviation gasoline Mineral spirits hydrochloric acid Methyl isobutyl ketone 8 50% sulfuric acid Acetone 20% nitric acid 5% acetic acid 30% sodium hydroxide Methanol Isopropanol Ethanol Oleic acid Chloroform 20% lactic acid Toluene After 24 hours immersion at 25 C., only 2 solvents had afl ected the films. These were acetone, which softened the film, and chloroform which softened and loosened the film. All other solvents and chemicals had no noticable effect. The immersion was continued until 7 days had passed at which time examination was again made. No further deterioration of the coatings on the probes was noted in any of the solvents or chemicals.

EXAMPLE E To 244.8 grams (0.234 mol) of the epoxy resin as used in Example B at C. was added 55.2 grams (0.234 mol) of the diacrylarnide adduct of piperazine of Example II. The temperature was raised to C. and after about 5 minutes at this temperature, the curing agent was dissolved in the epoxy resin and the mixture was quickly quenched.

After grinding to fine particle size the powder was checked for cure time. At 150 C. it cured in 7.0-7.5 minutes and at 205 C. in 3.5-4.0 minutes. A 3 gram pellet, 1%" diameter, flowed 7.37" down a 60 inclined hot plate held at 150 C. The films were hard and glossy when cured and gave good adhesion to steel. It would be useful as an epoxy film where hardness and adhesion were more important than firm flexibility.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A com-pound having the formula:

andnis1,2or3.

2. The compound of claim 1 where Z is (CH -R. 3. The compound of claim 2 where R is:

4. The compound of claim 2 where R is:

5. The compound having the formula:

9 10 6. The compound having the formula: 3,242,141 3/ 1966 Vertnick.

O CHFQH2 H Hoke X I] 3,377,303 4/1968 Peerman et a1. 260268 X ENC-CECE N'GHCHHN f, 3,385,858 5/1968 KatZ 260-268 CHr- H2 2 HrCNH2 5 DONALD G. DAVIS, Primary Examiner UNITED STATES PATENTS 'U.S. C1.X.R.

2,904,536 9/1959 Reith 260-268 X 106-47, 291, 99; 204-159.15; 2602, 290, 293, 348,

3,143,566 8/1964 Surrey 260-558 x 10 561 References Cited 

